Organic phosphorus compounds



amine derivatives or salts thereof.

compositions, etc. r

liatented Apr. 25, 1944 UNl TED STATES PATENT OFFICE Gennady M. Kosolapofl', Dayton, Ohio, assignor to Monsanto Chemical Company, a corporation of Delaware No Drawing.

ll Claims.

The present invention relates to new organic phosphorus containing compounds which have been found to have surface active properties.

The present compounds are new phosphinic acids of alkylated benzene hydrocarbons and They may be generally represented by the formula:

where R is an alkyl group of or more carbon atoms in length and R is hydrogen or a base, particularly a nitrogenous base.

The present group of alkylated aromatic phosphinate compounds are especially valuable as surface tension modifiers, particularly for the production of oil soluble emulsifying, wetting, dispersin'g and spreading agents for use in insecticides, emulsified paints, inks in dry cleaning As an example of the production of an alkyl aromatic phosphinic acid illustrating one form,

of my invention I react 265 g. of dodecyl benzene with 445 g. of P01: in the presence of 49g. of AlCla. This mixture may be refluxed for 5 days then extracted twice with 2 liters of hexone and the extracting solution then vacuum concentrated. The residue obtained upon concentration is poured upon ice and neutralized with NaOH in dilute solution. The solution is then filtered, acidified with HCl and can again be extracted with hexane followed by concentration.

The product, dodecyl benzenephosphinic acid, is.

obtained after evaporation of the hexane as a yellow oily acid, the yield is approximately 54% of theory.

In place of the dodecyl benzene described above I may carry out the same reaction using any of the alkylated benzene hydrocarbons, such as amyl benzene, hexyl benzene, heptyl'benzene, oc-

tyl benzene, nony1 benzene, 'decyl benzene, etc. The corresponding phosphinic acids in which the phosphorus is Joined to the aromaticresidue is obtained in good yields. These products are generally viscous yellow oils.

The above mentioned alkyl benzene phosphinic acids have pronounced acid qualities and I have found that they may be combined directly with Application May 7, 1941, Serial No. 392,898

, having the structure:

a nitrogenous organic base to produce stable, salts; Suitable organic bases are the amines which may be either primary, secondary or tertlary, hydroxy amines, or aromatic amines such as aniline, etc.

The following are examples of amine derivatives of my new phosphlnic acids:

Upon the addition of cyclohexylamine to dodecyl benzene phosphinic acid I obtain a yellow viscous liquid of pronounced water solubility having the chemical structure:

7-7- onnm H Water solutions of this derivative showed the following DuNouy surface tension, interracial ten-- sion, and spreading coefilcients: Concentration of solution per cent.-- 1 025 0.0625 Surface tension, dynes per cm 33.2- 32.7 33.6v Interracial tension, dynes per cm 1.5 I 1.4 2.0 Spreading coefllcient -0.2 +0.4 l.1

Upon the addition of-triethanolamine to dodecyl benzene phosphinic acid I obtain a yellowish thin wax of slight solubility in water, and

Upon the addition of dodecyl amine to dodecyl benzene phosphinic acid I obtain also a yello viscous liquid having the structure:

dodecyl benzene phosphinlc acid I obtain a water soluble product capable of forming a water solution of greatly reduced surface tension. The structure of this body is believed to be:

- or lithographic inks.

Water solutions of this derivative showed the following properties:

Concentration oi solution .per cent..- 1 0.0625 Surface tension, dynes per' cm; 31.6 31.6 32.8 Interracial tension, dynes per cm 1.0 1.4 1.7 Spreading coefflcient +1.9 +1.5 0.0

. matters in oils especially oils employed in making paints. varnishes. lacquers, enamels or printing What I claim is: I 1. Compounds having the structure:

where R is an alkyl group of at least 5 carbon atoms in length, and R is a nitrogenous base. 2. A dodecyl benzene phosphinic acid salt of a nitrogenous base.

3. A dodecyl benzene phosphinic acid salt of aniamlne.

4. The dodecyl benzene phosphinate salt of normal butyl amine.

5. The dodecyl benzene phosphinate salt oi cyclohexylamine.

6. The dodecyl benzene phosphinate salt of dodecyl amine. 7. The alkyl benzene phosphinio acid salt of normal butyl amine, in which the alkyl group contains at least 5 carbon 'atoms.

8. The alkyl benzene phosphinic acid salt of cyclohexylamine, in which the alkyl group contains at least 5 carbon atoms.

9. The alkylbenzene phosphinic acid salts of an amine, in which the alkyl group contains at least 5 carbon atoms.

10. The. alkylbenzene phosphinic acid salts of nitrogenous bases, in which the alkyl group contains at least 5 carbon atoms.

11. The alkylbenzene phosphinic acid salts of dodecyl amine, in which the alkyl group contains at least 5 carbon atoms.

GENNADY M. KOSOLAPOFF. 

